EP2201360B1 - Détection de substances chimiques par lumière infrarouge - Google Patents

Détection de substances chimiques par lumière infrarouge Download PDF

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EP2201360B1
EP2201360B1 EP08841350.5A EP08841350A EP2201360B1 EP 2201360 B1 EP2201360 B1 EP 2201360B1 EP 08841350 A EP08841350 A EP 08841350A EP 2201360 B1 EP2201360 B1 EP 2201360B1
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source
interest
analytes
laser
detection
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EP2201360A1 (fr
EP2201360A4 (fr
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R. Andrew Mcgill
Chris Kendziora
Robert Furstenberg
Michael Papantonakis
James S Horwitz
Graham K Hubler
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US Department of Navy
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma

Definitions

  • the present invention relates to explosive detection and more specifically to molecular or ion detection by selective thermal heating with incident infrared light resonant with one or more selected infrared absorption bands, and examination of IR radiation produced as a result of said incident light.
  • Pulsed laser surface fragmentation and mid-infrared laser spectroscopy for remote detection of explosives is discussed in C. Bauer et al., "Pulsed laser surface fragmentation and mid-infrared laser spectroscopy for remote detection of explosives," Appl. Phys. B., vol. 85, pages 251-256 (2006 ).
  • Generated product gases such as nitric oxide are probed by a synchronized distributed feedback quantum cascade laser (DFB-QCL) at ⁇ ⁇ 5.3 ⁇ m.
  • DFB-QCL distributed feedback quantum cascade laser
  • the ratio of NO and NO2 is a measure to distinguish between energetic and non-energetic materials.
  • the sampling techniques use non-selective removal of particles from a selected few surfaces which may have been contaminated with particles of explosives and transfer them onto a heated surface which is interfaced to an ion mobility spectrometer (IMS) or other explosive detection system (EDS).
  • IMS ion mobility spectrometer
  • EDS explosive detection system
  • Known methods of heating trace samples of explosives for detection purposes include broad band IR sources which heat in a non selective fashion. This approach consumes much more power than a selective heating process and generally heats everything incident with the heating source. This increases the general background level in the vapor phase of all the volatile chemicals in the material examined and can result in an increase in signal clutter or false alarms, especially when the substrate materials or additional contaminants being examined are of a complex natural origin such as leather, wood or food products.
  • LIBS Laser induced breakdown spectroscopy
  • the lasers used for LIBS are typically high power (10 mJ or greater) with short wavelengths (UV to near IR) and are not considered safe for environments where humans might be exposed or for the integrity of the substrate being examined.
  • LIBS is a type of atomic emission spectroscopy which utilizes a highly energetic laser pulse as the excitation source to ablate material, reducing it to its elemental constituents. LIBS can analyze any matter regardless of its physical state, be it solid, liquid or gas.
  • LIBS detects elements, its selectivity in the presence of many materials is suspect and is reliant on signal ratios of elements which can be confused when mixtures of materials are present.
  • Nitrogen for example, is present in many explosives but it is also prevalent in cotton or wool fiber or any proteinaceous material. Trace explosives present on natural fibers would be difficult to detect accurately with LIBS.
  • Raman spectroscopy is an emerging standard for optical identification and characterization of known and unknown samples. It couples to signature vibrational modes of the analyte and is complementary to infrared spectroscopy. Its main drawback is in its inefficiency because typically only one photon is Raman scattered for every million photons incident on the sample. Furthermore, Raman is isotropic, meaning there is no preferred direction for the scattered light to travel. This limits its application for stand off detection. For a fixed collection optic diameter, the photon collection efficiency decreases proportional to the second power of the distance to the sample under interrogation. Finally, Raman efficiency is optimized with high photon energy light which is not eye-safe to use in the presence of people.
  • Photo-thermal spectroscopy is another potential tool that is used in stand-off detection.
  • the sample is heated with a non-resonant, not eye-safe laser (usually visible wavelength of near-IR) in a periodic fashion (using a mechanical chopper).
  • the detected signal consists of the amplitude of the heated signal measured by an IR detector (or some other means) and its phase-angle shift with respect to laser heating.
  • This method differs from the present invention, in part, because it does not take advantage of the resonant nature of absorption of IR radiation which allows analyte selectivity right at the excitation stage and with much less laser power to achieve suitable heating.
  • a remote stand-off detection system is disclosed using a combination of pulsed laser fragmentation and pulsed mid-infrared laser absorption spectroscopy.
  • Generated product gases such as nitric oxide are probed by a synchronized distributed feedback quantum cascade laser at ⁇ 53 ⁇ m.
  • the ratio of NO and N02 is a measure to distinguish between energetic and non-energetic materials.
  • U.S. Patent No. 6,100,526 teaches that the concentrations of constituents of a sample of cereal grain or other agricultural product in a flowing stream can be determined while harvesting or processing using a short wave near infrared analyzer.
  • the analyzer irradiates the sample and then the diffused reflectance is analyzed.
  • the percentage constituents of the composite substance may then be compared with known percentage constituents to determine the constituents.
  • US 2006/023211A1 teaches a method for stand-off analysis of a sample comprising one or more chemical and/or biological warfare agents of low volatility.
  • the method uses a laser to vaporize the sample thereby producing a vapor plume of molecular species; and then uses an analytical means such as a reflective telescope to analyze the molecular species within the vapor plume based on the molecular emission spectra of the vapor plume.
  • this reference uses the stand-off analysis to detect methyl salicylate (example 1) and a liquid chemical warfare agent (example 2).
  • U.S. Patent No. 7,262,414 teaches a thermal luminescent (TL) spectroscopy system and method for remote sensing and detection of surface chemical contamination involving irradiation of a target surface with energy from a near infrared pump beam, and measurement of TL liberated by that surface within a middle infrared (MIR) region.
  • MIR middle infrared
  • the fundamental molecular vibration modes of target contaminants that are present are briefly activated after the surface has been driven out of thermal equilibrium.
  • An emissivity contrast between strata and target contaminant develops, peaks, and then subsides during a finite thermal window of detection in which detection of fingerprint identifiers for target contaminants is most probable.
  • Target contaminant identification employs neural network models trained and tested against known molecular absorption frequencies of target contaminants.
  • the use of a pump beam that radiates energy outside the MIR spectra of received TL reduces possible interference with the very weak MIR signals given off by target contaminants.
  • the performance of the optical technique was evaluated as a function of several variables, including the amount of contaminant, surface roughness the panel, and the presence of possible interfering species (such as water). Also, detection limits for generic hydrocarbon contaminants were evaluated as a function of system noise level.
  • One method of detecting explosives uses a broadband heating source connected to an IMS.
  • One problem with this method is that the entire composition of the surface, and possibly deeper, is heated which makes accurate detection of the analyte more difficult.
  • Another method of detecting explosives, narcotics and other chemical substances uses a laser source to ablate the particles, then collects them and subsequently analyzes them. Unfortunately, the ablation process may damage the analyte, resulting in additional signal clutter and possible reduction in the principle analyte signal, and this method requires a separate collection step.
  • the remote sensor could operate with an optical path length of 88 m or more than five times that of NDIR-UV instruments. Good agreement was obtained when comparing the TILDAS measurements with the on-board measurements of an instrumented HDDT. The distribution of NO emissions from HDDTs was found to be close to normal. Remote sensing of NO 2 emissions was demonstrated for the first time. The NO 2 emission factor determined in this study is consistent with other recent measurements. These emissions are underestimated in the EPA inventory, although part of the discrepancy can be explained by the effect of a "defeat device" that increases NO 2 emissions.”
  • the present invention has many advantages over the prior art. It may detect at stand off distances and be safely pointed at targets in areas with people present. It may selectively target materials in a complex matrix. It may detect at video frame rates or faster. It may be hand held. It may be operated without the persons present being cognizant of the ongoing detection process. It may efficiently vaporize or probe particles that are embedded in a surface such that they are difficult to remove using the normal physical rubbing or particle removal techniques.
  • photonic detection has several inherent advantages compared to other methods. These advantages include: an extremely high detection speed, zero interference with the existing radar and communication systems, and the potential for long range stand-off sensing. While several other all-optical techniques such as LIBS and Raman have been proposed for stand-off detection, these suffer from the fact that the wavelengths and intensities required are not safe to eyes and skin, or even to surfaces examined such as painted automobiles.
  • multispectral mode multispectral mode
  • a continuously tunable laser hyperspectral mode
  • further selectivity can be achieved by using a combination of resonant and/or non-resonant excitation.
  • further selectivity can be achieved by detecting only portions of the thermal band that is characteristic to the analyte of interest.
  • the present invention uses laser sources (e.g. QCLs) that are small, provide light that is invisible and safe to the human eye and are conducive to implementation in hand-held devices.
  • the transient response of the analyte to laser heating is measured instead of a response to periodic heating, thus providing a means for rapid detection as well as circumventing the problems associated with detection of loose powders/particles (such as explosives particulate residues) that are hard to detect using photothermal imaging due to long thermal constants.
  • This embodiment of the present invention may be stand-off, and provides advantages over currently available detection methods, especially compared to contact techniques that involve physical rubbing or air jetting of the substrate to remove solid particles of material to examine.
  • low vapor pressure analytes e.g., explosives, additives to explosives, drugs, chemical warfare agents, biochemicals, and biological warfare agents
  • analytes e.g., explosives, additives to explosives, drugs, chemical warfare agents, biochemicals, and biological warfare agents
  • particles of explosives or drugs are unwittingly transferred through fingerprints onto objects and surfaces that the person touches, or after a release of a chemical agent, the disseminated chemical is distributed onto a variety of surfaces as a trace residue.
  • the contaminated object or surface is excited (e.g., heated) actively and selectively by using an IR laser or a filtered light source so that a narrow wavelength range is used to be resonant with one or more selected absorption band(s) of the analyte of the nitrogen-oxygen bond.
  • Selective heating is used to maximize heating of the analyte of interest and to minimize heating or potential damage to materials that are not of interest to the detection application (e.g., substrate, contaminants), with the added benefit that significantly less laser power is needed.
  • the laser is coupled in a resonant fashion to one or more selected infrared absorption band(s) of the nitrogen-oxygen bond, to maximize the efficiency of energy transfer and to avoid electronically excited states that commonly lead to decomposition products.
  • Detecting the analyte of interest may be accomplished by using an IR camera.
  • An image taken before heating is e.g. compared to an image during heating.
  • the difference between the images or a differential image created by subtracting the image taken before from the image taken during heating can identify the presence of the analyte of interest.
  • FIG. 1 shows a schematic for one embodiment of the present invention.
  • FIG. 1(a) shows detection using an IR source and an IR detector.
  • the present invention provides a means to detect low vapor pressure analytes, such as explosives, drugs, and chemical agents, based on resonant absorption of certain infrared (IR) wavelengths.
  • IR infrared
  • Some examples of explosives or components of explosives that may be detected include 24DNT, TNT, RDX, HMX, TETRYL, PETN, NG, EGDN, DMNB, ammonium nitrate, urea nitrate and ANFO. simultaneously detect all organic energetic materials probed at a common wavelength and containing the nitrogen-oxygen bond (N-O), which is in the majority of the commonly used explosives (see FIG. 2 ).
  • N-O nitrogen-oxygen bond
  • the system can be tuned to a wavelength at or near a peak in the absorption spectrum characteristic of the nitrate ion
  • the N-0 band in the nitro group has natural resonance frequencies (symmetric and anti-symmetric) in the mid and long IR wavelengths.
  • the transmission spectra of organic based 24DNT, TNT and RDX chemicals shows that they exhibit a common absorption band near 6.25 ⁇ m as shown in FIG. 3 .
  • This N-0 stretch band and several others fortuitously fall in transmission windows of air (see FIG. 4 ), making them suitable for in air stand-off detection applications.
  • the vapor pressures of the majority of explosives are very low and typically well below a few parts per trillion at room temperature, traditional optical stand-off detection techniques applied to plumes of industrial chemicals or chemical agents are largely not useful. Additionally, the vapor pressure of explosives can be significantly reduced in composites containing explosives, such as C4, and masked due to complex packaging. However, the surface contamination of explosives and this persistence in the solid state can be exploited for stand-off detection by irradiating the explosive sample with the resonant absorption wavelength of the nitrogen-oxygen bond (indicated at 6.25 microns in FIG. 3 ) At these wavelengths, the coupling efficiency of the optical energy can be 1000 times greater than if the wavelength were just a few cm -1 away. Targeting any of these absorption peaks enables rapid, selective heating of the explosive material.
  • the thermal properties of the substrate on which the analyte is found are known, then the knowledge of both the degree of heating and the cooling time can be used as inputs in an alarm algorithm. For example, more heating at selected wavelengths on a metallic substrate such as a door knob (fast cooling) carries more weight (i.e. more likely to contain explosive residue) in an alarm algorithm than the same amount of heating on a plastic or fibrous substrate (slow cooling).
  • IR thermal imaging of a given scene is enhanced by illumination with an IR pulse (outside the camera detection wavelength range) to resonantly interact with the analyte or analytes of interest.
  • an IR pulse outside the camera detection wavelength range
  • a differential image with high fidelity can be generated which will distinctly identify explosive residue.
  • the resonant IR absorption wavelengths to use for heating should be common to explosives, but otherwise rare among possible substrate materials such as cotton, paper, plastics, metals etc. Further, by utilizing additional IR wavelengths, tests can be performed to probe for other types or classes of explosives as well as to increase system selectivity to confirm the type of explosive. In general, this approach offers advantages over other optical techniques in that it is eye-safe and compact.
  • Thermal imaging is enhanced by the heating signature due to the resonant absorption within the explosive residues of interest.
  • powerful mid-IR laser sources and sensitive IR focal plane arrays may be used. Both of these are commercially available today and should offer increased performance in upcoming years.
  • the IR source may be any source known in the art, such as a pulsed laser, continuous laser, broad band light source, filtered broad band light source, swept source, chirped source, variable source, or tunable source.
  • a quantum cascade laser may be used as the IR photon source.
  • QCL quantum cascade laser
  • the advantages of using QCL include: It can provide a single wavelength output allowing for the targeting of specific functional groups. It can operate at room temperature, and current devices can provide up to 1 Watt CW output, and it is commercially available. Moreover, a pulse is preferred over continuous wave (CW) for higher peak power, lower laser on times, and reduced cooling requirements. It is a stable laser source which in normal operation requires no consumable materials.
  • Any thermal imaging hardware comprising an IR camera (such as a commercial FLIR camera) can be used to collect and analyze long wave infrared (LWIR) light.
  • the advantages of this hardware include: it is a micro fabricated bolometer thermal imaging array, it is uncooled for low power operation, it responds to the 7-12 ⁇ m band which includes wavelengths generated from thermal heating, and it is small and lightweight.
  • a telescopic lens may be used to increase stand off distance capability.
  • the light entering the IR detector may be filtered to be selective for the analyte of interest.
  • the thermal emission spectra of analytes correlate with their absorption spectra.
  • a suitable optical filter can be designed which passes these analyte specific wavelengths and blocks all others. This way, only a signal attributable to the analyte is collected and the signal-to-noise ratio is increased. By combining both selective excitation and selective collection, the detection limit and detection selectivity of a given analyte can be greatly increased.
  • the present invention can be inherently eye-safe, with anticipated IR irradiances that are far below the maximum permissible exposure limit, which is of the order of 100 mW/cm 2 .
  • the maximum permissible exposure limit which is of the order of 100 mW/cm 2 .
  • many uses can be envisioned for this system, such as to not only scan suspected IEDs, but also to scan people (including for example: clothing, skin, glasses, shoes, hat, hair), airline boarding passes, vehicles, luggage, parcels, etc. Anything that a person handling explosives contacts is a suitable target.
  • Two or more lasers may be used to increase sensitivity and selectivity or expand the range of analytes examined.
  • Multiple lasers used in on- and off-resonance modes would improve the selectivity of the system by removing false positives which may occur because sometimes broadband absorbers heat independent of wavelength. Looking at the difference between the signals for on- and off-resonance with neighboring wavelengths will help remove effects from materials which are broad band IR absorbers and prevent false positives. If the difference between the two differential signals is negligible, the analyte of interest is concluded to be not present.
  • To compare the difference between signals on- and off-resonance compare either the difference of the differential signals or just the difference between the on- and off-resonance raw signals. The nature of the algorithm applied depends on the substrate material being examined.
  • the present invention is applicable in mobile and static applications.
  • the laser may be trained on a target so that as the detector/laser is moved the laser and camera remains trained on the target of interest.
  • targets which are mobile a static or mobile laser and camera can similarly be trained on the target of interest.
  • DMNB dimethylnitrobutane
  • a visible plume of material was ejected. Some of this material was collected on a neighboring substrate for characterization by FTIR. As shown in FIG. 5 , the collected material had the same spectral signature as the starting DMNB target material, proving that the laser energy was coupled into the DMNB without any significant chemical degradation. From a visual examination of the plume and the topography of the collected material, both vapor and particulate matter were ejected from the DMNB target. The laser intensity required to achieve these results was 30-40 microJ/cm 2 .
  • 24DNT 2,4-dinitrotoluene
  • the PEL tuned to 6.25 microns with 14 mJ pulses readily heated and partially vaporized the 24DNT slab (1 cm long) and 14 ms after a pulse from the laser a plume emitted is visible above the solid target.
  • a sequence of still stroboscopic back-illuminated photos was collected in close sequence to generate a video recording the effects of the laser on the sample of 24DNT.
  • One of the still photos is shown in FIG. 6 .
  • Some of the ejected material was collected on a neighboring substrate for further examination. Post analysis of the collected material confirmed that it had the same FTIR spectrum as the 24DNT target material. The laser energy was coupled into the 24DNT without any apparent decomposition.
  • a small trace sample of RDX deposited separately on planar polyethylene and gold substrates was positioned (under ambient laboratory conditions) in line with a quantum cascade laser (QCL) beam with an output wavelength of 6.30 microns.
  • the laser was focused to a spot size on the target of 1-2 mm 2 .
  • an infrared camera Photon Block 2 from FLIR, sensitive to light in the 7-12 micron range
  • RDX is a common explosive in land mines and other military ordnance.
  • the QCL allows a significant output power (>50 mW) to be achieved at the desired wavelength.
  • FIG. 7 shows the thermal image of RDX deposited as a trace quantity on a polyethylene substrate, illumination with QCL at 6.3 microns (5 mW/mm 2 ).
  • QCL QCL
  • the thermal conduction away from the RDX sample is higher. It is possible to see the thermal heating by inspection of the raw collected infrared image, but it was not as clear as the image collected on the polyethylene substrate.
  • a sequence of video frames was collected and a differential image was computed by subtracting the image directly before turning on the QCL with frames after turning on the QCL. Using this differential imaging approach, much clearer thermal image pictures were obtained to identify where the RDX was located, as shown in FIG. 8 .
  • the RDX By traversing or rastering the laser over the RDX deposited surface, the RDX could be mapped out over the entire surface examined.
  • the QCL light at 6.3 microns efficiently coupled into the RDX sample and thermally heated the sample by a few degrees, which was sufficient to generate IR light from the RDX.
  • the thermal image was captured with an uncooled microbolometer array IR detector (FUR Photon Block II).
  • the thermal heating of the RDX sample was very rapid and occurred within the time frame of the IR video used. At 30 frames/s, this indicates that significant thermal heating occurred in ⁇ 30 ms. Cooling after the laser exposure ends may occur over a longer time period. The cooling rates for the RDX (and other analytes) can aid in identifying the trace explosive material.
  • FIG. 9 shows the sample illuminated by a heatgun with no laser.
  • FIG. 10 shows the frequencies that were used in the example: ⁇ 1 was off-resonance for both TNT and RDX, ⁇ 2 was on-resonance for TNT but not RDX, ⁇ 3 was on-resonance for both RDX and TNT, and ⁇ 4 was on-resonance for RDX but not TNT. As shown in FIG.

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Claims (9)

  1. Système de détection de substance chimique sans contact d'un ou de plusieurs analytes d'intérêt qui sont des explosifs ayant une liaison azote-oxygène et qui sont situés sur une surface, comprenant :
    a. une source IR (IR SOURCE)
    b. un détecteur IR (IR DETECTOR) conçu pour recueillir un signal provenant de photons émis avant l'excitation du ou des analytes d'intérêt, et un signal provenant de photons émis pendant ou juste après l'excitation du ou des analytes d'intérêt ;
    c. un moyen permettant de comparer des signaux du détecteur IR (IR DETECTOR) recueillis à partir de photons émis par ledit détecteur IR,
    dans lequel ledit détecteur IR est une caméra IR, et
    dans lequel la source IR (IR SOURCE) est accordée au moins sur une bande d'absorption spécifique de la liaison azote-oxygène et est conçue pour exciter sélectivement, sans le(s) décomposer, le ou les analytes d'intérêt.
  2. Système selon la revendication 1, dans lequel la source IR (IR SOURCE) est sans danger pour l'œil humain.
  3. Système selon l'une quelconque des revendications 1 et 2, dans lequel la source IR (IR SOURCE) réduit au minimum le chauffage ou un endommagement potentiel d'un substrat sur lequel le ou les analytes d'intérêt sont situés.
  4. Système selon l'une quelconque des revendications 1 à 3, le système étant conçu pour être utilisé en respectant une distance de sécurité.
  5. Système selon l'une quelconque des revendications 1 à 4, dans lequel la source IR (IR SOURCE) est accordée sur des bandes d'absorption multiples spécifiques à des analytes d'intérêt multiples.
  6. Système selon l'une quelconque des revendications 1 à 4, dans lequel la source IR (IR SOURCE) est accordée sur des longueurs d'onde multiples, dans lequel au moins une longueur d'onde IR est en résonance avec l'analyte et au moins une longueur d'onde IR est hors résonance.
  7. Système selon l'une quelconque des revendications 1 à 6, dans lequel ledit moyen permettant de comparer des signaux IR comprend un microprocesseur (MICROPROCESSOR) conçu pour créer un signal différentiel en soustrayant le signal détecté provenant de photons émis avant l'excitation du ou des analytes d'intérêt du signal détecté provenant de photons émis pendant ou après l'excitation du ou des analytes d'intérêt.
  8. Système selon l'une quelconque des revendications 1 à 7, comprenant en outre un filtre optique qui laisse passer les longueurs d'onde dans la bande thermique où la détection se produit et bloque les longueurs d'onde du reste de la bande thermique.
  9. Procédé de détection de substance chimique sans contact à l'aide du système selon l'une quelconque des revendications 1 à 8, comprenant les étapes suivantes :
    a. l'excitation sélective d'un ou de plusieurs analytes d'intérêt, les analytes d'intérêt étant des explosifs ayant une liaison azote-oxygène et étant situés sur une surface, à l'aide de la source IR accordée sur au moins une bande d'absorption spécifique sans décomposer de manière significative l'analyte ; et
    b. la détermination du fait que l'analyte est présent ou non en comparant des photons émis à l'aide du signal de détection IR recueilli avant l'excitation de l'analyte et d'un signal du détecteur IR recueilli pendant ou juste après l'excitation de l'analyte.
EP08841350.5A 2007-10-24 2008-10-21 Détection de substances chimiques par lumière infrarouge Active EP2201360B1 (fr)

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US8421018B2 (en) 2013-04-16
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US20120091344A1 (en) 2012-04-19
US20120247230A1 (en) 2012-10-04
US8101915B2 (en) 2012-01-24
EP2201360A4 (fr) 2013-10-30
KR20100075500A (ko) 2010-07-02
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US20100044570A1 (en) 2010-02-25
KR101694717B1 (ko) 2017-01-10

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